Soil release chemicals and method of application to glass fabric or fiber

ABSTRACT

Soil release for application to glass fibers and fabrics which have been treated with acrylic resin, or acrylic resins, and dyes to give the fibers a base coat, which soil release comprises an aqueous emulsion of copolymers of acrylic or methacrylic acids with ester of acrylic or methacrylic acid, wherein the proportion of acid is high, ranging from about 25 to 80 percent acid, by weight, in combination with an aqueous solution of a nonyl or octyl phenol, reacted with from 9 to about 50 moles of ethylene oxide, and aqueous solution of a fatty alcohol or acid, which also has been reacted with 5 to 50 percent of ethylene oxide, the composition thus prepared being used as a finish bath treatment for glass fibers which have already been dyed or had a base color coating applied thereto, thereby to apply over the base color layer on a glass fiber or fabric a second molecular or semimolecular layer of this resinous material, which functions as a soil release and, also, by controlling the base dye system and amount of soil release obtain a fabric which is flame retardant.

United States Patent [72] Inventor William J. Cooney North Providence,R.l. [2]] Appl. No. 733,794 [22] Filed June 3,1968 [45] Patented Nov. 2,1971 [73] Assignee Chas. S. Tanner Co.

Warwick, RJ.

[54] SOIL RELEASE CHEMICALS AND METHOD OF APPLICATION TO GLASS FABRIC RFIBER 5 Claims, No Drawings [52] U.S.Cl 117/76 T, 117/139.5 A, 1 17/126GB, 117/126 GS [51] Int. Cl ..C03c /02, B32b 17/04 Field ofSearch117/126 GR, 126 GS, 76 T, 139.5 A

[56] References Cited UNITED STATES PATENTS 3,311,582 3/1967 Sparkseta]. 117/126X 3,444,116 5/1969 Gagnon et a1... 117/126X 3,476,580 ll/1969Jinnette 117/76 X Primary Examiner-William D. Martin AssistantExaminerD. Cohen Attorney-Thomas B. Graham ABSTRACT: Soil release forapplication to glass fibers and fabrics which have been treated withacrylic resin, or acrylic resins, and dyes to give the fibers a basecoat, which soil release comprises an aqueous emulsion of copolymers ofacrylic or methacrylic acids with ester of acrylic or methacrylic acid,wherein the proportion of acid is high, ranging from about 25 to 80percent acid, by weight, in combination with an aqueous solution of anonyl or octyl phenol, reacted with from 9 to about 50 moles of ethyleneoxide, and aqueous solution of a fatty alcohol or acid, which also hasbeen reacted with 5 to 50 percent of ethylene oxide, the compositionthus prepared being used as a finish bath treatment for glass fiberswhich have already been dyed or had a base color coating appliedthereto, thereby to apply over the base color layer on a glass fiber orfabric a second molecular or semimolecular layer of this resinousmaterial, which functions as a soil release and, also, by controllingthe base dye system and amount of soil release obtain a fabric which isflame retardant.

SOIL RELEASE CHEMICALS AND METHOD OF APPLICATION TO GLASS FABRIC ORFIBER THE BACKGROUND OF THE INVENTION Fabrics made of glass fiber havethe very desirable characteristic that they are durable and for use inpublic institutions as drapery fabrics, upholstery fabrics or astablecloths, they have the advantage of being nonflammable. They alsoinherently will not absorb soil, but itappears that the base surfacetreatments necessitated to permit coloring the fabrics will hold soiland also will be flammable, thereby neutralizing one of the advantagesof the glass. Hence, it is conventional on the textile industry toemploy formulations designed to impart some soil release characteristicto glass fiber fabrics, so that stains which in use are taken on by thefabrics can easily be removed by machine washing. However, accompanyingthe soil release characteristic of virtually all glass fibers, andfabrics made from glass fiber, is the flammability of the coatingmaterial. That is, generally, an organic resinous material and otherbalancing ingredients are used for the color coating and as aconsequence the inherent flammability of organic materials isencountered.

It is most desirable, that a finish applied over a fabric made of glassfiber be durable to machine washing and that it be one which gives goodsoil release characteristics. By this is meant that the stains normallyencountered in daily usage in such places as restaurants should beeasily removed. The property of soil release and nonflammabilitymeasured in terms of durability to machine washing should have a lifeapproximately that of the fabric, Furthermore, the fabric should showgood wrinkle recovery and, obviously, like any fabric used, it shouldhave a pleasant hand.

Of the collection of properties it is desirable to develop in the fabricthe one of nonflammability or nonflame propagation over the surface ofthe fabric is most important. lt has been noted, of course, that it isobvious that the glass fiber itself is not flammable. It is only thecoating material or the deposit fonned in surface treatment which willsupport combustion and will give the appearance of flammability to thefabric.

It is accordingly a fundamental object of this invention to provide asystem for treating glass fibers and fabrics to give them the virtues ofgood soil release which soil release has durability to washing, wrinklerecovery and and the other general physical characteristics desirablefor a textile, coupled with the fact that the fabric will not beflammable nor will the surface treatment be flammable or supportcombustion. Such a fabric will be virtually ideal for application as aupholstery fabric, drapery fabric, and tablecloth fabric for use inplaces of public assembly.

It is another object of the invention to provide a method for employingthese chemical treatments for the glass fabric, such that, even thoughthe chemicals themselves are flammable, their application under carefulconditions of the process on the fabric will induce the information of asurface finish having all the desirable properties of the soil releaseas well as nonflammability.

Other objects and advantages of the invention will in part be obviousand in part appear hereinafter.

DETAILED DESCRIPTION OF THE INVENTION In the description of theinvention herein it is to be understood that glass fibers and fabricsare used interchangeably and the chemistry is concerned with thesurfaces.

The theory of may finish for the glass fiber is to convert a lyophilicand hydrophobic surface, i.e., textile which is glass, to one which ishydrophilic, which conversion is done so that the fiber is wet by waterand surfactant preferentially, so that any oil or grease which may beadhering to its surface is removed. The finished system which I havedevised for accomplishing this result is based on the following:

In view of the fact that bare glass fibers as such will not retain thestains ordinarily encountered in use in domestic and publicinstallations it must be the pigment binding acrylic acid resins,softeners and coupling agents which form the carrying medium for a colorfinish in the glass surface which are the source of the problem. Thisfinish system or base coat, therefore, at its best must limit theeffectiveness of the finished surface to hold stains and, by appropriateapplication of base material to the glass fiber itself and overlayingthe base material with a hydrophilic system, I am able to achieve theresult that I develop all the properties useful for obtaining durabilityto machine washing and soil release, and I gain the extra bonus ofnonflammability of the surface finish on the fibers.

Accordingly, the system of preparing glass fabrics for soil release andnonflammability in accordance with this invention is basically atwo-step chemical treatment, followed by the conventional physicalfinishing. Fundamental to the operation is the two-step chemicalapplication of essentially two coats to glass fiber, the first stepbeing the application of a base finish as follows:

1. It consists of an acrylic latex essentially in the form of aqueousemulsion in water. Included with this is a softener which commonly willbe in the form of a silicone compound. A metal salt catalyst isincluded. Furthermore, a coupling agent and a pigment which can be anycolor used on the fabric is part of the bath composition. The whole isthen made up with water to the appropriate volume and concentration ofsolid ingredients. The base coat thus consists of an emulsion of waterand acrylic copolymers, glass reactive chemicals for adherence to theglass surface, silicone emulsion for softening, and may contain acommercial pigment dye. The base finish applied to a glass fabric bypadding gives the fabric its color and over this is applied a top finishwhich gives the property of soil release and nonflammability.

2. The top coat system is composed of three ingredients identified as anaqueous emulsion of an acrylic resin, as copolymer of acrylic ormethacrylic acids with esters of acrylic or methacrylic acids, whereinthe percentage of the acid is quite high, namely. ranging from about 25to percent acid, by mole percent, with a proportion of nonyl or octylphenol reacted with ethylene oxide; and a third component which consistsof a fatty alcohol or acid reacted with ethylene oxide. This compositionis prepared in relatively dilute fonn and should add no more than l to lA percent by weight of solids to the fabric so that total combinedsolids on the fabric contributed by the base coat (1) and top coat (2)does not exceed about 4 percent to 4% percent at this point.

In processing the fabric to apply the first coat the fabric is paddedthrough a bath carrying the acrylic binder, glass reactive chemical, andsoftener, and in appropriate cases a pigment dye; it is held at roomtemperature; the fabric is squeezed through pad rollers set at 40 lbs.per sq. inch and dried and cured at 350 F. C.) for 1% minute.

The second coat or the top coat is then applied to the fabric. Thesecond coat consists of acrylic and methacrylic acid with esters ofacrylic and methacrylic acids, wherein the percentage of the acids isquite high, nonyl phenol ethylene oxide condensate, and the fatty acidester or alcohol reacted with ethylene oxide. The second bath is appliedto the fabric at 50-122 F. (IO-50 C.), the fabric then is squeezedthrough pad rollers set at 30 lbs. per sq. inch and dried and cured at280-300F. (US-150C.) for IV: minute. Because the top coat containscertain volatile ingredients, it is necessary to pass the fabric througha hot water bath to render it noncombustible. Essentially this is merelyremoval of combustible volatile material.

Generally the fabric is best treated by passing it through a padder, aconventional piece of equipment in any textile treating plant, whichcontains water heated to about F. Generally the water bath should beclear and occasionally it calls for replacement to neutralize theaccumulation of volatiles from the padder.

EXAMPLE The processing of the fabric is best described in detail asfollows:

l. The base finish is applied to a conventional glass fiber fabric usinga conventional padder set for 30 to 50 pounds per sq. inch roll pressureon yarn fabrics of 401 gauge with 30 pounds per sq. inch for continuousyarn fabrics. After application of the base finish the fabric is rinsedand the finish is cured at 350 F. for approximately 1 f2 minutes.

2. The second, or top finish, is supplied using conventional paddingequipment set for about 30 to 50 pounds per sq. inch for the 401 yamfabrics or about 25 pounds per sq. inch for continuous yarn fabrics.

The finish is formulated as described in the following tabulation andthe finish, thereafter, is cured for 1 minutes at 280 F. to about 300 F.It is important to observe that the curing time and temperature are aninterval which is important to the development of the nonflammableproperty desired, because overcuring or undercuring will be detrimentalto the performance of the soil release coat finish.

3. Following the application of the soil release coat finish and itscure the material is passed through a hot water bath held atapproximately 190 F. and passed through a roll set for pressure about 30pounds per sq. inch. Fabric is then held at a temperature of275 F. for Iminutes or it is held at this temperature until it is dry.

By processing the fabric in this fashion I have found it possible todevelop through the use of the base coat the top coat and the finalhardening finish step a unified finish on the fabric, which ismanifested in a finished fabric characterized by the fact that it isnonflammable in the sense of not propagating flame and yet it retainsall the desirable characteristics of the fabric for use in conventionalinterior installations in places of public assembly.

A more detailed understanding of the invention can be had by referenceto the data in the following examples.

It is to be understood that the tabulation of the examples represents asequence of tests and that the techniques, wherever padding or dryingare referred to, are the conventional ones.

it is the composition of the coating bath, the finishing bath, and thetreatment steps related thereto and to each other which characterize theinvention;

Accordingly the following illustrative the properties which can bedeveloped in the glass fibers treated in accordance with the invention;

These materials form a durable soil release on glass fabric and byproper control of the ingredients a fabric that is flame retardant isproduced as indicated by the following:

EXAMPLES Woven fiber glass fabric was padded with the following coloringcompositions as a base coat:

No. I No. 2 No. 3 11 1:

Formula Padding Pigment Dispersion Yellow 2 Pink 2 White Acrylic Resin7.5 7.5 7.! Silicon: Softener l 10 IO Metal Salt Catalyst 1 1 Water 79.579.5 79.5

As catalyst, zinc nitrate, zinc chloride, magnesium chloride areaccepted as convenlional. They became effective at their disassociationtemperatures. i.e. about 325 The fiber glass was dried at about 250-300F. for l-l 2 minutes and cured at about 325 F. for about seconds. Thecatalyst salt disassociates forms acids, and induces reaction on thefibers. Then the base coated fabric was padded through the followingformulations:

Formula I: k k

Acrylic or Methacrylic emulsions Nonyl phenol ethylene oxide condensate4 2 l l 4 Fatty acid ester with ethylene oxide l The glass fabric wasdried at temperatures of 250 F. to 275 F. and then tested for soilrelease.

Fabric samples of about one yard square, where stained with butter,Wesson oil, Mazola, margerine, grape juice, (tomato) spaghetti sauce,mustard, salad dressing, beet juice, coffee, ketchup, and chocolate.These represent a good sampling of typical common soils encountered inrestaurants.

They were allowed to stand for over 30 minutes after being soiled andwashed in a home washing machine. The finish is durable to l5 washings.

All stains were removed.

Flammability with glass fibers is entirely a different problem fromflammability with natural fibers. The glass fiber will not burn, but inorder to obtain a desirable fabric it has to be dyed and treated withorganic chemicals. These chemicals in many cases can cause the fabric toappear to burn, but it is only the treatment chemicals which burn. inorder to produce a nonflammable soil release finish, it is necessarycarefully to control the materials applied in dyeing and the soilrelease finish.

Commercial soil release finishes now applied to glass fabric are usuallyvery flammable and do not use the materials specified herein.

In order to evaluate the flammability of the glass fabric treated inaccordance with my invention compared with commercially availablematerials, I used the following the tests:

No. l ASTM-D1230-6l (24) No.2 AATCC-33-l962 No. 3 AATCC-34-l966 No.4Modified AATCC-34-l966 Number 4 was a modification of AATCC-34-l966 inwhich the flame was one half inch long and was removed as soon as anyburning took place. Many materials which will not burn under testAATCC-34-l966 will burn completely up the whole length of sample underthe modified test. Under all these tests we also report surface scorch.

Fabric No. l designated in the following tests is a texturized Betaglass fabric dyed with formula No. 2 and soil release formula No. 2.

Fabric No. 2 designated in the following tests is a filament glassfabric dyed with formula No. 2 and soil release formula No. 1.

Fabric No. 3 is a commercial fiber glass fabric with a commercial soilrelease finish.

TEST METHOD ASTM-D 1 230-61 No. l DN No. 2 UN No. 3 I BE l" Circlecharred TEST METHOD AATCC-34-l 966 Fabric Surface After Flame After GlowChar Scorch Seconds Seconds Length No. l 1%" 2 y: No. 2 2 o a No. 3BURNED TO END OF FABRIC TEST METHOD MODIFIED AATCC-34-l966 Fabric AfterFlame After Glow Surface Seconds Seconds Char Ho. 1 l l 56" No. 2 l 1I82 No. 3 Burned The Complete Length of Fabric The above testsdemonstrate that a flame retardant fabric which will not supportcombustion can be produced with excellent soil release by proceeding inaccordance with my invention.

DESCRIPTION OF THE PADDING COMPOSITIONS For the preparation of the basecoat commercial Rhoplex resin emulsions sold by Rohm and Haas areuseful. They follow the composition pattern in the following tabulation.Essential to the base coat for holding the dye in place is that it be across linked, acrylic copolymer. Apparently this structure of polymerholds the dye particles in place. Hence, in the following tabulation thecombinations of ingredients among A through H are employed to provide abinder for the color pigment. The base coat material will not releasesoil and it will burn: Base Coat compositions:

No. I No. 2 No. 3

A Ethyl Acrylate' I6 20 22 6 Vinyl Acetate l4 C Bulyl Acrylate' I2 22 10D Methylol Acrylamide' 60% 2 2 4 E Hydroxy Ethyl Melhacrylale (30%) 0.50.5 I F Sodium Acetate 0.37 0.37 0.37 0 Potassium Persull'ate 0.19 0.19019 H Abex Ill-S 6.22 6.22 6.22. l Water 50 50 50 Water is put into aclosed reactor equipped with reflux then H and F are added. Three feedtanks are prepared. No. 1 has A, B and C mixed together. No. 2 has D andE mixed together. No. 3 has a solution of the catalyst G. Ten percentof'tank No. l and tank No. 2 are added to the reactor with agitation andit is heated to 140 to 150 F. and all tanks are then pumpedproportionate into the kettle over a period of 2 hours. The reaction isallowed to proceed until no more heat is generated the mixture iscooled.

Monomers The aqueous emulsion of water and copolymer of acrylic monomersfor the first coat, and for the second coat are available as commercialresin latices. One source is the sequence of acrylic resins sold as"Rhoplex" by Rohm and Haas.

in the top coat I prefer an aqueous emulsion or a copolymer of acrylicor methacrylic esters, wherein there is a relatively high proportion ofthe acid. These are combined with the emulsifier which is an aqueoussolution of alkyl phenol, nonyl or octyl phenol preferred, with 9 to 50moles of ethylene oxide in a preferred version.

The silicone softener is also a known item of commerce and may be anyone of the following: Arkolube Sil or an emulsion of a nonreactivesilicone.

The fatty acid ester emulsifier is that which has been described and isdefined in those terms. it is any fatty acid having eight to 20 carbonatoms, preferably those having l6 to 18 carbon atoms, such as stearic oroleic, reacted with ethylene oxide to the extent of taking up 10 to 50moles of the ethylene oxide. The proportions of these ingredients whichought to be combined together to form the bath for padding purposes arenot critical. It is important however, to have the bath of a totalsolids concentration for the padding technique, which is theconventional easy physical form of handling the materials to leavebehind on the fabric an appropriate quantity of the resin and the fireretarding agent. The total deposit should not exceed about 4 to 4percent of the weight of the fabric.

What is claimed is:

1. A soil release system for glass fiber surfaces comprising the glassfiber surface, a base coat on said surface, and a second nonflammablesoil release coat adhering to said base coat, whereby the finishedsystem is essentially nonflammable;

a. said base coat comprising a wash fast film dried and set on the bareglass fibers at a temperature of from 250-800 F., said film having beendeposited from an aqueous dispersion consisting essentially of across-linked acrylic resin polymer and a softener, and

b. said second coat having been deposited from an aqueous emulsion of l.a copolymer consisting of 25-80 mole percent of units derived fromethylenically unsaturated carboxylic acids or anhydrides and 20-75 molepercent of units derived from esters of acrylic or methacrylic acid 2. alower alkyl phenol reacted with 9-50 moles of ethylene oxide, and

3. the reaction product of a fatty acid or fatty alcohol having from8-26 carbon atoms with from 5-50 mole percent of ethylene oxide,

and set at a temperature of about 350 F.

2. A system according to claim 1 where the concentration of the acrylicor methacrylic copolymer in the second coating is between 1 percent and5 percent of the emulsion.

3. A system according to claim 1 wherein the emulsifier is nonyl oroctyl phenol reacted with 9 to 50 moles of ethylene oxide, and is in thecoating at a concentration between onefourth and 10 percent on theweight ofthe solution.

4. A system according to claim 1 wherein the fatty acid or alcohol makesup between 0 to 10 percent of the weight of the solution.

5. A glass fabric characterized by its soil release system and itsnonfiammability comprising a fabric of texturized filament glass fiberssaid fabric carrying thereon a first coat and a second coat, said firstcoat comprising a film formed from a composition of l. 0.5 to 5 percentofa pigment padding dispersion,

2. 3 to l2 percent of a cross-linking acrylic emulsion that is durableto washing 3. 3 to l0 percent of a nonreactive silicone emulsion 4. 0.5to 2 percent ofa metal salt catalyst and bonding agent for glass 5. withwater to make percent which composition is deposited on said fabric andcured, and

wherein said first coat total add on of solids does not exceed 3 percentof the weight of the fibers;

said coat being set at a temperature of 250800 F., and

a second coat to impart soil release and nonflammability comprising theingredients 1. 5 to 20 percent of an emulsion of a copolymer consistingof 25-80 mole percent of units derived from ethylenically unsaturatedcarboxylic acids or anhydrides and 20-75 mole percent of units derivedfrom esters of acrylic or methacrylic acid,

2. 0 to 4 percent of a nonyl phenol with 9 to 50 moles ethylene oxidereacted therewith.

3. to 4 percent of a fatty acid ester of 6 to 28 carbons reacted with to50 percent ethylene oxide,

where the amounts of solids add on of said second coat does not exceed 1to h percent on the weight of the fibers, and said coat being set at atemperature of about 350 F 5

2. A system according to claim 1 where the concentration of the acrylicor methacrylic copolymer in the second coating is between 1 percent and5 percent of the emulsion.
 2. 3 to 12 percent of a cross-linking acrylicemulsion that is durable to washing
 2. a lower alkyl phenol reacted with9- 50 moles of ethylene oxide, and
 2. 0 to 4 percent of a nonyl phenolwith 9 to 50 moles ethylene oxide reacted therewith.
 3. 0 to 4 percentof a fatty acid ester of 6 to 28 carbons reacted with 5 to 50 percentethylene oxide, where the amounts of solids add on of said second coatdoes not exceed 1 to 1/2 percent on the weight of the fibers, and saidcoat being set at a temperature of about 350* F.
 3. the reaction productof a fatty acid or fatty alcohol having from 8- 26 carbon atoms withfrom 5- 50 mole percent of ethylene oxide, and set at a temperature ofabout 350* F.
 3. 3 to 10 percent of a nonreactive silicone emulsion
 3. Asystem according to claim 1 wherein the emulsifier is nonyl or octylphenol reacted with 9 to 50 moles of ethylene oxide, and is in thecoating at a concentration between one-fourth and 10 percent on theweight of the solution.
 4. A system according to claim 1 wherein thefatty acid or alcohol makes up between 0 to 10 percent of the weight ofthe solution.
 4. 0.5 to 2 percent of a metal salt catalyst and bondingagent for glass
 5. with water to make 100 percent which composition isdeposited on said fabric and cured, and wherein said first coat totaladd on of solids does not exceed 3 percent of the weight of the fibers;said coat being set at a temperature of 250* -800* F., and a second coatto impart soil release and nonflammability comprising the ingredients 5.A glass fabric characterized by its soil release system and itsnonflammability comprising a fabric of texturized filament glass fiberssaid fabric carrying thereon a first coat and a second coat, said firstcoat comprising a film formed from a composition of